Acrylic aminimides



United States Patent 3,527,802 ACRYLIC AMINIMIDES Robert C. Slagel,Savage, Minn., assignor to Ashland Oil & Refining Company, Ashland, Ky.,a corporation of Kentucky No Drawing. Continuation-impart of applicationSer. No. 514,705, Dec. 15, 1965. This application May 5, 1967, Ser. No.636,273

Int. Cl. C07c 103/44 US. Cl. 260-561 6 Claims ABSTRACT OF THE DISCLOSUREAcrylic aminimides are prepared from acrylic acids or derivativesthereof. The acrylic aminimides can be homopolymerized and copolymerizedto result in functional group-containing polymeric products capable ofthermosetting. The acrylic aminimides have the general formula:

R R wasting.

wherein R is a hydrogen, lower alkyl (C -C aryl, chlorine, fluorine,bromine, or cyano group and R R and R are hydrocarbon radicals and R andR can be combined to form a heterocyclic ring with the nitrogen.

This application is a continuation-in-part of Ser. No. 514,705 filedDec. 15, 1965.

The present invention relates to novel acrylic amin imides and topolymers thereof. In another aspect, the present invention relates toprocesses for the preparation of the acrylic aminimides, theirpolymerization, and the subsequent chemical modification of suchpolymers.

The acrylic aminimides of the present invention have the generalformula:

wherein R is a hydrogen, lower alkyl (C -C aryl, chlorine, fluorine,bromine, or cyano group, R and R are aliphatic or aryl hydrocarbonradicals having from 1 to 22 carbon atoms or radicals in which R and Rare combined to form heterocyclic rings with the nitro gen, and whereinR is a saturated or unsaturated aliphatic hydrocarbon radical of 1 to 22carbon atoms. The term aryl as employed herein is meant to define anaromatic radical in which the unsatisfied valence is at a carbon atom ofthe aromatic nucleus. The term acrylic will be understood as beinggeneric to the type of compound defined by the foregoing formula.

The novel aminimides of the present invention are prepared by either oneof two methods. In the first method, the aminimide is prepared byreacting a hydrazine with an acrylic acid chloride in the presence of aninert organic solvent, subsequently reacting the resulting hydrazideWith a quaternizing agent to form the hydrazinium salt, and thendehydrohalogenating the reaction 3,527,802 Patented Sept. 8, 1970 'icein which R, R R and R have the above-indicated meaning, and X can be anysuitable anion.

The unsymmetrical hydrazine employed in the formation of the aminimidesof the present invention can be obtained by the reaction of a halo-aminewith a tertiary amine, resulting in the hydrazinium salt which isreacted with a base to form the hydrazine. Since the reaction is wellknown in the art, no further description is deemed necessary.

The unsymmetrical hydrazine is reacted with the acrylic acid chloride inthe presence of an inert solvent such as benzene, dimethyl sulfoxide,acetonitrile, dioxane, tetrahydrofuran, ethers, e.g. diethyl ether,glymes (i.e., dimethyl ethers of ethylene glycol), and the like. Thesolvent is employed in suflicient amounts to allow the formation of afluid reaction mixture. Preferably, the reaction is conducted at ambienttemperature and pressure conditions, although higher and lowertemperatures or higher and lower pressures can be employed if called forby the reagents employed in the particular synthesis. In general, thereaction conditions employed should provide for the removal of theby-product HCl. Although the reaction proceeds rapidly, it is generallypreferred to employ longer reaction times to assure completion of thereaction and thereby higher yields of the hydrazide. An excess of eitherreagent can be employed, although such is not necessary in View of thequantitative yields obtained by the use of nearly equivalent amounts ofthe acid chloride and the hydrazine. The hydrazide may precipitate outof the solvent, depending on the solvent. If the hydrazide does notprecipitate, it can be readily isolated by evaporation of the solvent.

The hydrazide is quaternized with a compound having the general formula:R X, wherein R is a saturated or unsaturated aliphatic hydrocarbonradical and preferably a lower alkyl radical, and X can be anyquaternizing anion but is preferably an aryl sulfonate radical or ahalogen radical such as chlorine, bromine or iodine.

Suitable quaternizing agents, therefore, include methyl chloride, methylbromide, ethyl chloride, methyl iodide, propyl chloride, ethyl bromide,methyl benzene sulfonate, methyl toluene sulfonate (methyl tosylate),and ethyl toluene sulfonate.

The reaction of the hydrazide with the quaternizing agent is preferablyconducted in the presence of a solvent which is generally of the type ofinert solvent hereinabove indicated and is also employed in the sameamounts. Re action temperatures will vary from room temperature toelevated temperatures which do not cause the decomposition of thereagents or products. The solution obtained in the formation of thehydrazide can be directly employed in the described quaternization.

The hydrazinium salt is dissolved in water or an alcohol such asmethanol, and dehydrohalogenated to the aminimide by titrating with analcoholic base to a neutral end point. Preferred bases are the alkalimetal bases such as sodium hydroxide or potassium hydroxide. Theaminimide is isolated by precipitating the alkali metal salt andevaporating the solvent.

The unsymmetrical hydrazine, which is reacted with the acrylic acidchloride to form the acrylic hydrazine,

has the general formula:

H /R1 \NN\ 11/ R2 wherein R and R have the above-indicated meaning.

Preferably, R and R are lower alkyl groups, phenyl or substituted phenylgroups, or together with the nitrogen form such heterocyclic ringcompounds as pyrrolidine, pyrrole, pyrroline, or piperidine. Specificexamples of the unsymmetrical hydrazines employed include dimethylhydrazines, diethyl hydrazine, methyl-ethyl hydrazine, dibutylhydrazine, N-amino-Z-phenyl pyrrolidine, phenylmethyl hydrazine,diphenyl hydrazine, and dicresyl hydrazine.

The acrylic acid chlorides employed in the present invention are formedfrom the acrylic acids which are well-known in the art. The acidchloride is formed from the acid by reaction with excess benzoylchloride or thionyl chloride at room temperature. The acid chloride canalso be prepared by reacting the sodium salt of the acrylic acid withoxalyl chloride in benzene.

Suitable acrylic acid chlorides include acrylyl chloride, methacrylylchloride, ethacrylyl chloride, a-phenylacrylyl chloride, u-chloroacrylylchloride, a-fluoroacrylyl chloride, and a-cyanoacrylyl chloride.

In the alternate way of preparing the novel aminimides, a hydraziniumsalt is reacted with an alkyl ester of the acrylic acid in the presenceof a base in accordance with the following reaction scheme:

wherein R and R to R have the above-indicated meaning, and X is aradical capable of forming an anion and preferably is a sulfonateradical or a halogen, e.g. chlorine, iodine, or bromine. R; can be analkyl radical of 1 to 22 carbon atoms but preferably is a lower alkylradical of 1 to 6 carbon atoms. The base is preferably a strong basesuch as a metal alkoxide, e.g. sodium alkoxide or an alkali metalhydroxide, e.g. sodium hydroxide or potassium hydroxide. The reaction ispreferably carried out in an organic solvent such as tetrahydrofuran,methanol, isopropanol, t-butanol, benzene, and the like.

The hydrazinium salt employed in the formation of the aminimide can beobtained by the reaction of a haloamine and a tertiary amine. Thehalo-amine has the general formula: NH X, wherein X is a halogen, e.g.chlorine or bromine. Ordinarily, X is chlorine and the chloroamine isobtained by the reaction of ammonia with chlorine. This reaction ispreformed at temperatures of from 20 to 100 C. and at pressures of to100 p.s.i. Preferably, the reaction is conducted in the vapor phase andpreferably an excess of ammonia is used.

The tertiary amine which can be reacted with a haloamine to produce thehydrazinium salt is an amine having the formula: NR R R wherein R R andR have the above-indicated meaning. The reaction of tertiary amine andhalo-amine is usually conducted by bubbling the haloamine in gaseousform through the tertiary amine which is usually in liquid form at roomtemperature in atmospheric pressure.

The hydrazinium salt can also be obtained by the reaction of anunsymmetrical hydrazine and a quaternizing agent having the formula: RX, wherein R has the aboveindicated meaning, and X can be anyquaternizing anion, but is preferably an aryl sulfonate radical or ahalogen such as chlorine, bromine or iodine. Suitable unsymmetricalhydrazines which can be employed in the formation of the hydraziniumsalt have been set forth hereinabove.

The reaction of the unsymmetrical hydrazine with the quaternizing agentcan be conducted in the absence of a solvent or, if a homogenous liquidmixture of the reagent can be formed, in the presence of a diluent whichis generally a non-polar solvent such as carbon disulfide or benzene.Alternatively, the reaction can also be carried out in a polar solventsuch as isopropanol, methanol, or tbutanol. The reaction temperature canvary from room temperature to elevated temperatures which do not causedecomposition of the reagents or products. Generally, the reaction iscarried out at room temperature.

The hydrazinium salt is then reacted with the ester in the presence of abase and preferably in the presence of a polar solvent of the typedescribed hereinabove, such as an alcohol, to produce the aminimide.Preformed hydrazinium salt solutions can similarly be employed in thesynthesis of the aminimide. The reaction mixture is then evaporated andthe aminimide can be extracted with a suitable solvent or with thereaction solvent which does not cause appreciable solution of theby-product of the cation of the base with the anion of the quaternarysalt.

Various methods can be employed to purify the resulting aminimides suchas extraction followed by crystallization, precipitation, sublimation,evaporation, or chromatographic or ion exchange separation.

The reaction of the ester with the hydrazinium salt or solution thereofis carried out at temperatures maintained in the range between 0 and 150C. and preferably between 20 and 60 C. Although both lower and higherpressures can be used, it is preferred to conduct the reaction atatmospheric pressure. The preferred solvents are alcohols such astertiary butanol and isopropanol. The reagents, i.e., the ester, thehydrazinium salt, and the base, are employed in essentially equimolarratios, although such is not critical. In general, sufiicient solvent isemployed to allow the formation of a liquid mixture and preferably from500 to 1000 ml. per mole of reactants is used. The time of reaction mayvary from 1 minute to 12 hours and generally it is in the range of 2 to5 hours.

Aminimides which can be prepared by the described processes includetrimethylamine acrylimide, trimethylamine methacrylimide,dimethyl-ethylamine acrylimide, diethylmethylamine methacrylimide,triethylamine methacrylimide, dipropylmethylamine acrylimide,tributylamine acrylimide, phenyl-dimethylamine acrylimide, N-methylpyrrol acrylimide, N-methylpyrrol methacrylimide, N-ethylpyrrolineacrylimide, N-ethylpyrroline methacrylimide, N-phenylpyrrolineacrylimide, trimethylamine a-chloroacrylimide, trimethylamineethacrylimide, trimethylamine a-phenylacrylimide, trimethylaminea-cyanoacrylimide, and triethylamine a-ChlOl'O- acrylimide.

The novel acrylic aminimides of the present invention can be polymerizedthrough addition to the double bond. In general, the polymerization iscarried out in a polar medium such as water or acrylonitrile using afree radical polymerization initiator such as an aZo-bis-nitrile or aperoxide. In view of the instability of the aminimide group attemperatures above 150 C., as more specifically explained hereinbelow,polymerization temperatures are within the range of 25 to 120 C. andpreferably within the range of 60 to C. The polymerization catalyst isemployed in concentrations normally employed in the polymerization ofvinyl monomers. Polymerization times will vary depending on thepolymerization temperature, the concentration and type of initiator, andthe degree of conversion of monomer to polymer desired. Completeconversion of monomer to polymer may require several days under mildconditions.

The aminimides can furthermore be copolymerized in all ratios with vinylmonomers such as other acrylic monomers, vinyl esters, vinyl halides,and vinyl aromatic monomers. The term acrylic monomers is defined asincluding monomers containing the structure:

wherein R has the above-indicated meaning. Suitable acrylic comonomersfor the aminimides of the present invention include ethyl acrylate,methyl 'acrylate, buty1 acrylate, methyl methacrylate, ethylmethacrylate, hydroxy substituted alkyl acrylates and methacrylates suchas hydroxy ethyl methacrylate, hydroxy propyl methacrylate, and thecorresponding acrylates, alkoxy substituted alkyl acrylates andmethacrylates such as methoxy ethyl acrylate and methoxy ethylmethacrylate and the like. The copolymerization can be conducted in bulkor in a common solvent at temperatures of 25 to 120 C. using a peroxide,an azo-bis-nitrile, or similar free radical initiator.

The utility of the polymers and copolymers of the present invention isbased on their ability to be converted to polyisocyanates which have awell-established utility in the formation of polyurethanes. Theconversion is generally accomplished by pyrolysis. The conversion isillustrated by the following equation:

lid

in which R and R to R have the above-indicated meaning.

The tertiary amine by-products are well-known catalysts in thepolymerization of isocyanates with hydroxylterminated polyesters,polyethers and polyols.

Pyrolysis of the aminimide in monomeric or polymeric form can beconducted by heating the aminimide to temperatures above about 150 C.,and results in the formation of the isocyanate and a tertiary amine bythe above equation.

Although it is possible to convert the aminimide of the presentinvention to the isocyanate prior to polymerization, it is generallypreferred to convert the aminimide subsequent to polymerization in viewof the greater chemical stability of the aminimide group as compared tothe isocyanate group. This is particularly significant in the formationof urethane linkages in the sense that the aminimide can be admixed withpolyhydroxy compounds and form a stable system. On heating such system,the aminimide is converted to the isocyanate, which reacts with thepolyhydroxy compound, while simultaneously releasing a tertiary amine,which acts as a catalyst for the reaction of the isocyanate with thepolyhydroxy compound. It will be apparent, therefore, that theincorporation of a small number of the novel aminimide monomers into anotherwise unreactive polymer (i.e., containing no isocyanate groups orZerewitinoff hydrogen) converts such polymer chains into a crosslinkablesystem which can be crosslinked with a curing agent, i.e., an agentwhich contains two or more Zerewitinolf hydrogens. The meaning of theterm Zerewitinolf hydrogen is wellestablished in the polyurethane artand includes, in particular, the hydroxyl group. The polymer systems ofthe present invention have the additional advantage of being stable attemperatures below 150 C. in the presence of compounds containing aZerewitinofi hydrogen. The use of the homopolymers and copolymers of thepresent invention alone or in combination with other compatible resinsin coating vehicles not only permits the crosslinking of such coatingvehicles on heating if such coating vehicles contain the necessaryhydroxyl groups, but furthermore would allow the chemical bonding of thecoating to the substrate if such substrate contains reactive hydroxylgrou s. Additionally, the presence of the polar group introduced by theaminimide will result in better bonding to polar substrates by virtue ofthe attraction of the two groups even in the absence of chemicalreaction.

The polymers of the present invention which contain a higher number ofaminimide units have utility in polyurethane systems which are wellknown in the art. The acrylic aminimide can furthermore be converted tothe isocyanate and then employed directly in polyurethane systems,thereby introducing reactive double bonds into the system.

The foregoing discussion of the utility of the aminimides of the presentinvention and their polymers is not intended to limit the utility of theaminimides to such, since many other applications will be apparent tothose skilled in the art from the dual reactivity of the aminimides.

An alternative way of preparing the novel polymers of the aminimides ofthe present invention comprises the polymerization of the acrylichydrazinium salt using the above-described techniques followed byconversion of the hydrazinium salt to the aminimide polymer again usingthe techniques hereinabove described.

The formation of the novel aminimides, their polymerization, and theirconversion to isocyanates is further illustrated by the followingexamples in which all units of quantity are by weight unless otherwisestated.

EXAMPLE 1 To 2 64 g. (4.3 moles) of unsymmetrical dimethyl hydrazine intwo liters of cold benzene is added 208 g. (20 moles) of methacrylylchloride with stirring. After two hours, the addition is completed and ayellow solid precipitates out. The reaction mixture is warmed to roomtemperature and the product is filtered. The product is extracted fourtimes with 1 liter portions of warm benzene. Evaporation of the benzeneextract in vacuo results in 137.4 g. (53%) of 1,1-dimethyl-2-methacrylylhydrazine, a white solid having a melting point of 67 to 70 C. Onrecrystallization, the product melts at 73 C. The infrared spectrum ofthe product shows a NH absorption band at 3200 cmf double bondabsorption at 3040 and 1630 CHI-T1, and amide carbonyl absorptions at1670 and 1540 CITITI.

In 225 ml. of acetonitrile is dissolved 20.0 g. (0.154 mole) of the1,1-dimethyl-2-methacrylyl hydrazine and 28.6 g. (1.54 moles) ofmethyl-ptoluene sulfonate. The reaction mixture is agitated and refluxedfor six hours. On cooling to room temperature,2-methacrylyl-1,1,1-trimethyl hydrazinium p-toluene sulfonatecrystallizes out of the reaction mixture. The product obtained weighs32.2 g. (68%), and has a melting point of 150 to 151 C. On evaporationof the solvent, an additional 15 g. of the sulfonate is obtained.

The 2-methacrylyl-1,1,1-trimethyl hydrazinium p-toluene sulfonate isdissolved in ml. of distilled water and 10% sodium hydroxide solution isadded until a phenophthalein end point is reached. Evaporation of thewater in vacuo results in a white solid which is extracted with warmchloroform. Evaporation of the chloroform results in 9.0 g.(quantitative) of trimethylamine methacrylylimide having a melting pointof 149 to 152 C. On recrystallization from hexane, the product has amelting point of 149 to 150 C. Infrared and nuclear magnetic resonanceanalyses confirm the structure of the product.

Analysis.Calculated for CqHmNgO (percent): C, 59.12; H, 9.92; N, 19.70.Found (percent): C, 59.24; H, 9.89; N, 19.54.

EXAMPLE 2 To 75 ml. of tertiary butanol is added 11.0 g. (0.1 mole) oftrimethyl hydrazinium chloride, 10.0 g. (0.1 mole) of methylmethacrylate, and 5.4 g. (0.1 mole) of sodium methoxide. The temperatureof the reaction mixture is increased to 48 C. and kept at 48 C. for sixhours with agitation. The reaction mixture is then pressure filtered toremove the salt formed. On evaporation of the filtrate in vacuo, 11 g.(78% yield) of trimethylamine methacrylimide is obtained. Onrecrystallization from benzene, the product is found to have a meltingpoint of 149 to 150 C.

EXAMPLE 3 To a solution of 264 g. (4.3 moles) of unsymmetrical dimethylhydrazine in 2 liters of cold benz ne is added 181 g. (2.0 moles) ofacrylyl chloride. On completion of the addition (4 hours), a yellowsolid precipitates out of the reaction mixture. The reaction mixture isallowed to warm to room temperature and suction filtered. The solid isthen extracted four times with one liter portions of warm benzene. Onevaporation of the benzene in vacuum, 54.6 g. of a white solid isobtained having a melting point of 77 to 83 C. Recrystallization withhexane results in 34.9 g. of 1,1-dimethyl-2-acrylyl hydrazine having amelting point of 86 to 87 C. Infrared analysis confirms the structure ofthe product obtained.

To 25 g. (0.22 mole) of 1,1-dimethyl-2-acrylyl hydrazine in 170 g. ofacetonitrile is added 31.0 g. (0.22 mole) of iodomethane. The reactionmixture is refluxed with stirring for 3 hours. On removal of the solventin vacuo, 54.8 g. (98% yield) of 2-acrylyl-1,1,1-trimethyl hydraziniumiodide, a pale yellow solid having a melting point of 128 to 133 C., isobtained.

A solution of 50 g. of 2-acrylyl-1,1,1-trimethyl hydrazinium iodide in80 ml. of distilled water is prepared and sodium hydroxide solution isadded until a phenophthalein end point is reached. On evaporation agummy solid is obtained which is extracted with chloroform using aSoxhlet extractor. Evaporation of the chloroform results in 23.9 g.(95%) of a yellow solid. Sublimation of this product results intrimethylamine acrylimide, a white crystalline product having a meltingpoint of 102 to 104 C. Infrared and nuclear magnetic resonance analysesconfirm the structure of the product.

Analysis.Calculated for C H N O (percent): C, 56.27; H, 9.37; N, 21.86.Found (percent): C, 56.10; H, 9.53; N, 21.28.

EXAMPLE 4 In 75 ml. of tertiary butanol is placed 8.6 g. (0.1 mole) ofmethyl acrylate, 11.0 g. (0.1 mole) of trimethyl hydrazinium chloride,and 5.4 g. of sodium methoxide. The reaction mixture is agitated andheated at 45 C. for seven hours. On filtration of the salt formed, thereaction mixture is evaporated to give 11.4 g. (89%) of viscous yellowliquid which crystallizes on standing. Vacuum sublimation of thecrystalline solid results in trimethylamine acrylimide.

EXAMPLE 5 In parts of distilled water is dissolved 3.7 parts oftrimethylamine methacrylimide and 0.1% (based on monomer) ofazo-bis-isobutyronitrile dissolved in 1 part of acetone is added. Thereaction vessel is purged with nitrogen and the temperature of thereaction mixture is increased to 82 C., at which temperature the mixtureis held for 2.25 hours under nitrogen. The reaction mixture is cooled toroom temperature and poured into parts of acetone. A white solidprecipitates. On drying over phosphorus pentoxide at C., 1.9 parts of awhite homopolymer of trimethylamine methacrylimide is obtained. Infraredanalysis of the polymer shows strong absorption at 1565 cm.-corresponding to the aminimide carbonyl band. Nuclear magnetic resonanceanalysis also confirms the structure of the polymer, On heating totemperatures of 176 C., the aminimide groups in the polymer areconverted to isocyanate groups.

EXAMPLE 6 In 14 parts of Water is dissolved 5 parts of2-methacrylyl-1,1,1-trimethyl hydrazinium-p-toluene sulfonate and 0.1%of azo-bis-isobutyronitrile dissolved in 1 part of acetone is added. Thereaction vessel is purged with nitrogen and the temperature of thereaction mixture is increased to 82 C., at which temperature thereaction mixture is maintained for 6 hours under nitrogen. The reactionmixture is then poured into 200 parts of acetone with stirring. Theresulting fine, white precipitate is filtered, washed repeatedly withhot acetone and dried in vacuum over phosphorus pentoxide to result in0.5 part of a homopolymer of 2-methacrylyl-1,1,1-trimethylhydrazinium-p-toluene sulfonate. Infrared and nuclear magnetic resonanceanalyses confirm the structure of the polymer.

The polymer is dissolved in about 15 parts of distilled water and 10%sodium hydroxide solution is added until the phenophthalein end point isreached. The solution is then evaporated to near dryness in vacuo andpoured into excess acetone which precipitates a white solid identifiedas the homopolymer of trimethylamine methacrylimide. Infrared andnuclear magnetic resonance analyses confirm the structure of thehomopolymer.

EXAMPLE 7 In 6.3 parts of methyl methacrylate is dissolved 1 part oftrimethylamine methacrylimide and 0.2% of azo-bisisobutyronitrile in 0.5part of methyl methacrylate is added to the mixture. The reaction vesselis purged with nitrogen and the reaction mixture is heated to C. for 1.5hours under nitrogen. The polymerized reaction mixture is added toexcess acetone, causing a solid precipitate to form which is washed withmethanol. The resulting polymer is crushed and dried at C. The polymeris dissolved in chloroform and drawn on a glass plate to form a hard,colorless film that remains clear when baked in an oven at C. for 16hours. Infrared and nuclear magnetic resonance analyses confirm thestructure of the polymer to be a copolymer of trimethylaminemethacrylimide and methyl methacrylate containing 10% of trimethylaminemethacrylimide and 90% of methyl methacrylate. On heating of thecopolymer to a temperature of 175 C., the aminimide groups are convertedto isocyanate groups.

EXAMPLE 8 Trimethylamine methacrylimide, 1.4 parts, is dissolved in 5.5parts of warm vinyl acetate and 0.2% of azo-bisisobutyronitriledissolved in 1.0 part of vinyl acetate is added. The reaction vessel ispurged with nitrogen and the reaction mixture is heated to 70 C. andmaintained at 70 C. for 12 hours under a flow of nitrogen. The reactionproduct is steam distilled and subsequently heated with chloroform. Awhite solid polymer is obtained on cooling the chloroform solution whichis washed and dried. A part of the chloroform solution containing about30% of polymer is drawn on a glass plate and allowed to dry. A clearfilm is obtained. Infrared and nuclear magnetic resonance analyses ofthe film indicate the polymer to be a copolymer of trimethylaminemethacrylimide and vinyl acetate, containing about 30% of trimethylaminemethacrylimide and 70% of vinyl acetate. On heating the polymer to aboutC., the aminimide groups are converted to isocyanate groups.

9 EXAMPLE 9 I Into a pressure reaction vessel is charged 2 parts oftrimethylamine methacrylimide and 30 parts of methyl ethyl ketone. Thereaction vessel is cooled to below 75 C. in an acetone-Dry Ice bath and23.3 parts of vinyl chloride is added together with 0.02 part ofazo-bis-isobutyronitrile. The vessel is sealed and brought to atemperature of 50 to 60 C., at which temperature the reaction mixture isagitated for a period of 20 hours. The vessel is then cooled again to--75 C., opened and allowed to come to room temperature. The polymerprecipitates out of the reaction mixture and is separated and dried.Infrared analysis confirms vinyl chloride and trimethylaminemethacrylimide as being incorporated into the polymer, and nuclearmagnetic resonance and microanalyses demonstrates the copolymer oftrimethylamine methacrylimide and vinyl chloride to contain thecomonomers in a ratio of 3 to 1 of vinyl chloride to trimethylaminemethacrylimide.

EXAMPLE 10 Into a 100 ml. serum bottle is charged, under nitrogen, a 75ml. solution of 0.03 g. of azo-bis-isobutyronitrile, 7.11 g. (0.05 mole)of trimethylamine methacrylimide, 10.60 g. (0.20 mole) of acrylonitrilein purified acetoninitrile. The bottle is sealed and suspended in awater bath maintained at 70 C. for 2 hours. The bottle is then ventedand opened and the contents poured into ether in a Waring Blendor. Theprecipitate is collected by filtration, washed with ether, and driedunder high vacuum. A solid copolymer of acrylonitrile and trimethylaminemethacrylimide containing about 33.5% of the aminimide is obtained andweighs 1.1 g.

EXAMPLE 11 Into a 150 ml. reactor equipped with stirrer, N bubbler,condenser and addition funnel is placed 50 ml. of acetonitrile and 0.5g. of azo-bis-isobutyronitrile. The reactor is sealed and flushed withnitrogen and the temperature brought to 80 to 90 C. To the reactionmixture is then added, over one hour, a solution containing 8 g. oftrimethylamine methacrylimide, 4 g. of hydroxy propyl methacrylate, and28 g. of methyl methacrylate. Heating is continued for an additionalhour. A solid terpolymer of methyl methacrylate, hydroxy propylmethacrylate, and trimethylamine methacrylimide (53%) in a monomer ratioof 9: 1:1 respectively is obtained.

On heating to 165 C., trimethylamine is liberated from the terpolymerwith formation of isocyanate groups. A 50% solution of the terpolymer inacetone is prepared and a 3 mil film is drawn down. The film is allowedto air dry for two days, and is found to have a Sward hardness of 42 to43. The film is then heated to 170 C. for 15 minutes. Evolution oftrimethylamine is noted during heating. The Sward hardness of the heatedfilm increases to 54 to 55, indicating the formation of a cross-linkedpolymer. Infrared analysis indicates the presence of urethane linkagesin the heated terpolymer.

EXAMPLE 12 Into a 1-liter, S-neck flask equipped with a stirrer, refluxcondenser, temperature controller probe, addition funnel, and N bubblingtube 255 parts of water are added, stirred and flushed with N for 15minutes. At this time, 42 parts of an anionic surfactant, such as Abex183, is added and dissolved. Ten percent of the monomer mixture (150parts of ethyl acrylate, 17 parts of trimethylamine methacrylimide, 50parts of hydroxypropyl methacrylate, and 80 parts of methylmethacrylate) is added and flushed. The reaction vessel is put under a Npressure of 20 bubbles per minute, and heated to 70 C. At this point,3.0 parts of K 0 are added and the reaction is allowed to initiate. Theaddition of the remainder of the monomers is continued over a one hourperiod.

The polymer is purified by precipitating in water and by severalwashings with water. An interpolymer of the four monomers is obtained.The monomer ratio in the polymer is approximately 19: 10: 1:1, of ethylacrylate to methyl methacrylate to hydroxypropyl methacrylate totrimethylamine methacrylimide respectively. The molecular weight of thepolymer is about 11,200.

EXAMPLE 13 Into a 3-neck, 250 ml. stirred flask equipped with a refluxcondenser and temperature controller is added g. of acetonitrile. Tothis solvent is added 7.3 g. of trimethylamine methacrylimide, 25 g. ofmethyl methacrylate, and 5.5 mg. of azo-bis-isobutyronitrile which isthen flushed with N for 15 minutes at approximately 200 bubbles perminute.

The flask is then placed under N pressure and heated to 80 C. for twohours. The polymer is purified by precipitation in water stirred by aWaring Blendor, redissolved in acetone, and precipitated again in aWaring Blendor with water, followed by five water washes. A solidcopolymer of methyl methacrylate and trimethylamine methacrylimidehaving a molecular weight of about 5,600 is obtained. The monomer ratioin the copolymer is approximately 20 methyl methacrylate units to 1trimethylamine methacrylimide unit.

EXAMPLE 14 Condensed into a 1-liter Parr bomb which has been flushedwith nitrogen, cooled to 75 C. in a Dry Iceacetone bath and flushed withvinyl chloride, are 167 parts of vinyl chloride. The sealed bomb is thenplaced in the heater and the stirrer is turned on at 400 500 r.p.m.

Separately, a solution is prepared containing 844 parts of water, 6parts of conc. NH OH, 0.20 part of AgNO 3.0 parts of K S O 40.0 parts oftrimethylamine methacrylimide, and 18.0 parts of an anionic surfactant,such as dodecylbenzene sodium sulfonate.

When the bomb and vinyl chloride reach room temperature, 52.5 parts ofthe above emulsion are added under pressure. The bomb contents are thenheated to 50 C. and maintained at that temperature for about 12 hours.Excess vinyl chloride is then vented and a solid copolymer of vinylchloride and trimethylamine methacrylimide is obtained on coagulationand filtration of the reaction mixture.

EXAMPLE 1S Into a reactor equipped with a stirred dropping funnel,stirrer, Dry Ice trap, and vacuum line is charged 250 ml. of dibutylphthalate. The dibutyl phthalate is heated to 170 C. in vacuo of 50 mm.Hg. To this is added 250 ml. of dibutyl phthalate containing, insuspended form, 27.5 g. (1.93 moles) of trimethylamine methacrylimideover a period of 45 minutes. A light yellow liquid is collected in thetrap. Redistillation of the liquid results in 7.7 g. (48%) of clearliquid. The infrared spectrum shows the compound to contain both anisocyanate group and ethylenic unsaturation.

The foregoing examples have illustrated the preparation of the novelaminimides of the present invention, the formation of homoand copolymersfrom the aminimides, and the conversion of the polymeric aminimides toisocyanate group-containing polymeric materials. It will be apparentthat the foregoing illustrated methods of preparing and polymerizing theaminimide can similarly be employed in the preparation andpolymerization of other aminimides coming within the scope of thepresent invention. Other methods of polymerizing the aminimides of thepresent invention as well as the formation of other types of copolymersof the aminimides will be apparent from the foregoing specificillustrations.

1 1 What is claimed is: 1. A compound of the formula:

wherein R is hydrogen, a lower alkyl group, phenyl, chlorine, fluorine,bromine, or a cyano group, R R and R when taken singly, represent aphenyl or an alkyl radical having from 1-22 carbon atoms and whereincarbon atoms and wherein R and R when taken collectively with thenitrogen atom to which they are attached, represent a heterocyclic ringselected from the group consisting of pyrrolidine, pyrrole, pyrrolineand piperidine.

2. The aminimide of claim 1 wherein R is hydrogen or a lower alkyl.

3. The aminirnide of claim 2 wherein R R and R are lower alkyl radicals.

4. The aminimide of claim 2 wherein R R and R are methyl.

5. The aminimide of claim 1 wherein R, R R and R are methyl.

6. The aminimide of claim 1 wherein R is hydrogen and R R and R aremethyl.

References Cited UNITED STATES PATENTS 3,410,880 11/1968 Brocklehurst260104.5

ALEX MAZEL, Primary Examiner J. A. NARCAVAGE, Assistant Examiner US. Cl.X.R.

